EP2103651A1 - Vinyl chloride resin composition - Google Patents

Vinyl chloride resin composition Download PDF

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Publication number
EP2103651A1
EP2103651A1 EP07832512A EP07832512A EP2103651A1 EP 2103651 A1 EP2103651 A1 EP 2103651A1 EP 07832512 A EP07832512 A EP 07832512A EP 07832512 A EP07832512 A EP 07832512A EP 2103651 A1 EP2103651 A1 EP 2103651A1
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EP
European Patent Office
Prior art keywords
vinyl chloride
chloride resin
resin composition
acid
butyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP07832512A
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German (de)
French (fr)
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EP2103651A4 (en
Inventor
Satsuki Hasegawa
Masashi Harada
Masaru Nagahama
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Adeka Corp
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Adeka Corp
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Publication of EP2103651A1 publication Critical patent/EP2103651A1/en
Publication of EP2103651A4 publication Critical patent/EP2103651A4/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating

Definitions

  • the present invention relates to a vinyl chloride resin composition (hereinafter also referred to simply as "resin composition”) and, more particularly, to a vinyl chloride resin composition having improved electrical resistance.
  • Vinyl chloride resin has excellent electrical insulating properties, high arc resistance, high tracking resistance, and high withstanding voltage and is therefore very important as an insulating material, as compared with rubber and polyolefins.
  • the excellent characteristics of vinyl chloride resin deteriorate owing to thermal and oxidative degradation, and therefore vinyl chloride resin becomes unusable for practical applications.
  • various stabilizers have been added to vinyl chloride resin insulating materials.
  • lead stabilizers such as tribasic lead sulphate and lead stearate, have been used. These stabilizers are excellent heat stabilizers and have advantages, such as relatively low prices.
  • lead stabilizers have high toxicity and insufficient electrical insulating properties. In particular, the electrical insulating properties of lead stabilizers deteriorate with increasing temperature of an insulator.
  • low-toxic stabilizers alone have insufficient stabilizing effect and are practically used in combination with various additive agents that improve resistance to light, heat, and oxidation, such as an organic phosphite compound, epoxy compound, or phenol antioxidant, a benzophenone or benzotriazole ultraviolet absorber, and a hindered amine light stabilizer.
  • Patent Document 1 discloses a vinyl chloride resin composition that contains a hydrotalcite compound and an alkaline earth metal or aluminum silicate.
  • Patent Document 2 discloses a vinyl chloride resin composition that contains a hydrotalcite compound and an aluminosilicate compound of an alkaline earth metal salt.
  • a composition that contains calcium carbonate and 0.5 parts by weight of silicate per 100 parts by weight of a vinyl chloride resin has a volume resistivity of about 20 x 10 12 ⁇ cm.
  • existing vinyl chloride resin compositions have insufficient electrical insulating properties.
  • a vinyl chloride resin composition according to the present invention contains 0.1 to 3 parts by weight of synthetic aluminum silicate per 100 parts by weight of a vinyl chloride resin, the synthetic aluminum silicate having an apparent specific gravity of 7 ml/g or more.
  • the synthetic aluminum silicate preferably has a specific surface area of 400 m 2 /g or more.
  • a wire coating material according to the present invention contains the vinyl chloride resin composition according to the present invention.
  • the present invention can provide a vinyl chloride resin composition having a high electrical resistance.
  • Use of the vinyl chloride resin composition can provide a wire coating material having excellent electrical insulating properties.
  • a vinyl chloride resin composition according to the present invention will be described in detail below.
  • a vinyl chloride resin used in the present invention can be prepared by any method, including bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.
  • the vinyl chloride resin include polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-ethylene copolymer, a vinyl chloride-propylene copolymer, a vinyl chloride-styrene copolymer, a vinyl chloride-isobutylene copolymer, a vinyl chloride-vinylidene chloride copolymer, a vinyl chloride-styrene-maleic anhydride terpolymer, a vinyl chloride-styrene-acrylonitrile copolymer, a vinyl chloride-butadiene copolymer, a vinyl chloride-isoprene copolymer, a vinyl chlor
  • a vinyl chloride homopolymer (polyvinyl chloride) is particularly preferred.
  • Use of polyvinyl chloride can provide a material having flexibility, high flame resistance, and excellent processibility.
  • a synthetic aluminum silicate having an apparent specific gravity of 7 ml/g or more used in the present invention may be any synthetic aluminum silicate having the specified apparent specific gravity and may be a commercial product, such as Kyoward 700 (manufactured by Kyowa Chemical Industry Co., Ltd.). Use of synthetic aluminum silicate having an apparent specific gravity of 7 ml/g or more can significantly improve the electrical resistance of the resin composition.
  • the synthetic aluminum silicate has an apparent specific gravity in the range of 8 to 10 ml/g.
  • the synthetic aluminum silicate has a specific surface area of 400 m 2 /g or more. It is assumed that such synthetic aluminum silicate can efficiently trap impurities that reduce the electrical resistance in the resin. More preferably, the synthetic aluminum silicate has a specific surface area in the range of 500 to 800 m 2 /g.
  • the content of synthetic aluminum silicate in the resin composition according to the present invention ranges from 0.1 to 3 parts by weight, preferably 0.2 to 1 part by weight, per 100 parts by weight of a vinyl chloride resin. At a content of synthetic aluminum silicate below 0.1 parts by weight, the electrical resistance is not sufficiently improved. On the other hand, at a content of synthetic aluminum silicate above 3 parts by weight, the electrical resistance is not significantly improved, and the color of the resin composition deteriorates.
  • a vinyl chloride resin composition according to the present invention may contain a plasticizer, a metal salt compound, such as a barium-zinc stabilizer, a calcium-zinc stabilizer, a tin stabilizer, or a lead stabilizer, a hydrotalcite compound, a ⁇ -diketone compound, perchlorate, an organic phosphite compound, a phenol or sulfur antioxidant, an epoxy compound, a polyol compound, a hindered amine compound, an ultraviolet absorber, a filler, and a stabilization aid, which are commonly used in vinyl chloride resin compositions.
  • a plasticizer such as a barium-zinc stabilizer, a calcium-zinc stabilizer, a tin stabilizer, or a lead stabilizer, a hydrotalcite compound, a ⁇ -diketone compound, perchlorate, an organic phosphite compound, a phenol or sulfur antioxidant, an epoxy compound, a polyol compound, a hindered amine compound, an ultraviolet absorb
  • the plasticizer may be a plasticizer commonly used for vinyl chloride resin and includes phthalate plasticizers, such as dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, dilauryl phthalate, ditridecyl phthalate, dioctadecyl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate; adipate plasticizers, such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, and di(butyl diglycol) adipate; phosphate plasticizers, such as triphenyl phosphate, tricresyl phosphate,
  • the amount of the plasticizer generally ranges from 30 to 100 parts by weight, preferably 40 to 80 parts by weight, more preferably 45 to 70 parts by weight, per 100 parts by weight of a vinyl chloride resin. Less than 30 parts by weight of the plasticizer may have insufficient plasticizing effect. On the other hand, more than 100 parts by weight of the plasticizer may result in insufficient strength of the resulting vinyl chloride resin composition, and therefore the vinyl chloride resin composition may become unusable for practical applications.
  • the metal salt compound examples include organic carboxylates, such as stearates, laurates, oleates, maleate, and benzoates, phosphates, such as stearyl phosphate, distearyl phosphate, phenyl phosphate, and diphenyl phosphate, and basic salts, carbonates, and sulfates thereof, and basic salts, metal oxides, and metal hydroxides thereof. These compounds may be used alone or as a mixture thereof, or occasionally a complex thereof.
  • the hydrotalcite compound is preferably a double salt compound composed of magnesium and/or zinc and aluminum having the following general formula (I). Water of crystallization of the hydrotalcite compound may be removed.
  • the hydrotalcite compound may be a natural or synthetic compound.
  • the synthetic compound may be prepared by a known synthesis method described in Japanese Examined Patent Application Publications No. 46-2280 , 50-30039 , 51-29129 , 3-36839 , as well as Japanese Unexamined Patent Application Publications No. 61-174270 , 2001-164042 , 2002-53722 and the like.
  • the hydrotalcite compound may have any crystal structure and any crystal particle size. Residual heavy metals, such as iron, in the raw materials of the hydrotalcite compound are preferably minimized at practical refining costs.
  • the hydrotalcite compound may be coated with a higher fatty acid, such as stearic acid, a higher fatty acid metal salt, such as an alkali metal oleate, an organic sulfonate metal salt, such as an alkali metal salt of dodecylbenzenesulfonic acid, a higher fatty acid amide, a higher fatty acid ester, or wax.
  • a higher fatty acid such as stearic acid
  • a higher fatty acid metal salt such as an alkali metal oleate
  • an organic sulfonate metal salt such as an alkali metal salt of dodecylbenzenesulfonic acid, a higher fatty acid amide, a higher fatty acid ester, or wax.
  • ⁇ -diketone compound examples include acetylacetone, triacetylmethane, 2,4,6-heptatrione, butanoylacetylmethane, lauroylacetylmethane, palmitoylacetylmethane, stearoylacetylmethane, phenylacetylacetylmethane, dicyclohexylcarbonylmethane, benzoylformylmethane, benzoylacetylmethane, dibenzoylmethane, octylbenzoylmethane, bis(4-octylbenzoyl)methane, benzoyldiacetylmethane, 4-methoxybenzoylbenzoylmethane, bis(4-carboxymethylbenzoyl)methane, 2-carboxymethylbenzoylacetyloctylmethane, dehydroacetic acid, cyclohexane
  • Metal salts of these ⁇ -diketone compounds may also be used.
  • metals for use in ⁇ -diketone metal salts include alkali metals, such as lithium, sodium, and potassium; alkaline earth metals, such as magnesium, calcium, strontium, and barium; and zinc, aluminum, tin, and alkyltin.
  • perchlorate examples include sodium perchlorate, potassium perchlorate, barium perchlorate, ammonium perchlorate, and hydrotalcite treated with perchloric acid.
  • organic phosphite compound examples include triphenyl phosphite, tris(2,4-ditert-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, tris(mono- and di-nonylphenyl) phosphite, diphenyl acid phosphite, 2,2'-methylenebis(4,6-ditert-butylphenyl)2-ethylhexyl phosphite, diphenyldecyl phosphite, phenyldiisodecyl phosphite, tributyl phosphite, tris(2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphi
  • phenol antioxidant examples include 2,6-ditert-butyl-4-methylphenol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl(3,5-ditert-butyl-4-hydroxyphenyl) propionate, distearyl(3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene bis[(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2-methyl-4,6-bis(octylthiomethyl)phenol, 2-(3,5-ditert-butyl-4-hydroxyphenyl)amino-4,6-bis(octylthio)-s-triazine, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid
  • sulfur antioxidant examples include dialkyl thiodipropionate, such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and myristylstearyl thiodipropionate, and ⁇ -alkyl mercaptopropionates of polyols, such as pentaerythritol tetra(3-dodecyl mercaptopropionate).
  • dialkyl thiodipropionate such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and myristylstearyl thiodipropionate
  • ⁇ -alkyl mercaptopropionates of polyols such as pentaerythritol tetra(3-dodecyl mercapto
  • epoxy compound examples include epoxidized animal and vegetable oils, such as epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, and epoxidized safflower oil, epoxidized methyl stearate, epoxidized butyl stearate, epoxidized 2-ethylhexyl stearate, epoxidized stearyl stearate, epoxidized polybutadiene, tris(epoxypropyl) isocyanurate, epoxidized tall oil fatty acid esters, epoxidized linseed oil fatty acid esters, bisphenol A diglycidyl ether, vinylcyclohexene diepoxide, dicyclohexene diepoxide, and 3,4-epoxycyclohexylmethyl-3,4
  • polyol compound examples include trimethylolpropane, ditrimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, and polypentaerythritol, partial esters of these polyol compounds and fatty acids, such as stearic acid, bis(dipentaerythritol) adipate, tris(2-hydroxyethyl) isocyanurate, and saccharides, such as sorbitol and mannitol.
  • hindered amine compound examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) ⁇ di(tridec
  • ultraviolet absorber examples include benzotriazoles, such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-ditert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole, and 2,2'-methylenebis(4-tert-octyl-6-benzotriazolyl)phenol; 2-hydroxybenzophenones, such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); benzoates, such as phenyl salicylate, resorcinol
  • the filler examples include calcium carbonate (heavy, light, and precipitated), gypsum, titanium oxide, barium sulfate, alumina, hydrocalumite, sodium silicate, magnesium silicate, aluminum silicate, calcium silicate, zeolite, silica stone, diatomaceous earth, activated clay, talc, mica, clay, colcothar, rock wool, graphite, and carbon black.
  • calcium carbonate is preferred because of its insignificant adverse effect on the weatherability of a vinyl chloride resin.
  • the stabilization aid examples include diphenylthiourea, anilinodithiotriazine, melamine, benzoic acid, cinnamic acid, p-tert-butylbenzoic acid, anhydrous silicic acid, silicate, and zeolite.
  • a resin composition according to the present invention may contain additive agents commonly used for vinyl chloride resin, for example, a cross-linker, an antistatic agent, an anti-fogging agent, an anti-plate-out agent, a surface-treating agent, a lubricant, a flame retardant, a fluorescent agent, a fungicide, a bactericide, a foaming agent, a metal deactivator, a mold-release agent, a pigment, a processing aid, an antioxidant, and a light stabilizer.
  • additive agents commonly used for vinyl chloride resin for example, a cross-linker, an antistatic agent, an anti-fogging agent, an anti-plate-out agent, a surface-treating agent, a lubricant, a flame retardant, a fluorescent agent, a fungicide, a bactericide, a foaming agent, a metal deactivator, a mold-release agent, a pigment, a processing aid, an antioxidant, and a light stabilizer.
  • a resin composition according to the present invention can be used independently of the method for processing a vinyl chloride resin and can be preferably used, for example, in roll processing, extrusion, casting, and pressure forming.
  • a vinyl chloride resin composition according to the present invention can be preferably used as a wire coating material and exhibit excellent electrical insulating properties.
  • a compound shown in Table 1 was kneaded with a rolling mill at 160°C and 30 rpm for 5 minutes and was pressed at 190°C for 5 minutes to form a sheet having a thickness of 1 mm.
  • a test specimen was prepared from the sheet and was subjected to a volume resistivity test (VR) [ ⁇ cm] in accordance with JIS K 6723.
  • Table 2 shows the results.
  • [Table 1] Compound Parts by weight Vinyl chloride resin 100 Diisononyl phthalate 50 Heavy calcium carbonate 20 Hydrotalcite 3.5 Zinc stearate 0.7 Dibenzoylmethane 0.1 Tetrakis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane 0.1 Sorbitol 0.05 Inorganic additive agent shown in Table 2 See Table 2
  • Example 1 and Comparative Example 1 in Table 1 clearly show that synthetic aluminum silicate having an apparent specific gravity of 7 ml/g or more significantly improves the volume resistivity, as compared with synthetic aluminum silicate having a small apparent specific gravity.
  • the results of Example 2 and Comparative Example 2 show that this tendency is enhanced with an increase in the content of synthetic aluminum silicate.
  • synthetic aluminum silicate having an apparent specific gravity of 7 ml/g or more is an excellent electrical resistance improver for vinyl chloride resin.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
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Abstract

A vinyl chloride resin composition that has better electrical insulating properties than existing vinyl chloride resin compositions and a wire coating material that includes the vinyl chloride resin composition are provided.
A vinyl chloride resin composition contains 0.1 to 3 parts by weight of synthetic aluminum silicate per 100 parts by weight of a vinyl chloride resin, the synthetic aluminum silicate having an apparent specific gravity of 7 ml/g or more. Synthetic aluminum silicate having a specific surface area of 400 m2/g or more can be preferably used. The wire coating material contains the vinyl chloride resin composition.

Description

    Technical Field
  • The present invention relates to a vinyl chloride resin composition (hereinafter also referred to simply as "resin composition") and, more particularly, to a vinyl chloride resin composition having improved electrical resistance.
    • Background Art
  • Vinyl chloride resin has excellent electrical insulating properties, high arc resistance, high tracking resistance, and high withstanding voltage and is therefore very important as an insulating material, as compared with rubber and polyolefins. However, the excellent characteristics of vinyl chloride resin deteriorate owing to thermal and oxidative degradation, and therefore vinyl chloride resin becomes unusable for practical applications.
  • To overcome these drawbacks, various stabilizers have been added to vinyl chloride resin insulating materials. Among others, lead stabilizers, such as tribasic lead sulphate and lead stearate, have been used. These stabilizers are excellent heat stabilizers and have advantages, such as relatively low prices. However, lead stabilizers have high toxicity and insufficient electrical insulating properties. In particular, the electrical insulating properties of lead stabilizers deteriorate with increasing temperature of an insulator.
  • Thus, lead stabilizers have recently been substituted by barium-zinc stabilizers and calcium-zinc stabilizers. However, low-toxic stabilizers alone have insufficient stabilizing effect and are practically used in combination with various additive agents that improve resistance to light, heat, and oxidation, such as an organic phosphite compound, epoxy compound, or phenol antioxidant, a benzophenone or benzotriazole ultraviolet absorber, and a hindered amine light stabilizer.
  • Although inorganic compounds or polyols have been used as electrical insulation improvers, these improvers have a limited improving effect. Thus, there has been a demand for a material that can substitute these known electrical insulation improvers. However, such a material has not been found.
  • For example, Patent Document 1 discloses a vinyl chloride resin composition that contains a hydrotalcite compound and an alkaline earth metal or aluminum silicate. Patent Document 2 discloses a vinyl chloride resin composition that contains a hydrotalcite compound and an aluminosilicate compound of an alkaline earth metal salt. However, for example, a composition that contains calcium carbonate and 0.5 parts by weight of silicate per 100 parts by weight of a vinyl chloride resin has a volume resistivity of about 20 x 1012 Ωcm. Thus, existing vinyl chloride resin compositions have insufficient electrical insulating properties.
    • Patent Document 1: Japanese Unexamined Patent Application Publication No. 5-179090 (Claim)
    • Patent Document 2: Japanese Unexamined Patent Application Publication No. 8-109297 (Claim)
    Disclosure of Invention Problems to be solved by the Invention
  • As described above, since vinyl chloride resin insulating materials heretofore studied are not satisfactory, there is a demand for a vinyl chloride resin composition having improved electrical insulating properties.
  • Accordingly, it is an object of the present invention to solve the problems described above and provide a vinyl chloride resin composition that has better electrical insulating properties than existing vinyl chloride resin compositions.
    • Means for Solving the Problems
  • As a result of diligent and repeated investigations, the present inventors completed the present invention by finding that the problems described above can be solved by incorporating particular synthetic aluminum silicate into a vinyl chloride resin.
  • That is, a vinyl chloride resin composition according to the present invention contains 0.1 to 3 parts by weight of synthetic aluminum silicate per 100 parts by weight of a vinyl chloride resin, the synthetic aluminum silicate having an apparent specific gravity of 7 ml/g or more. In a resin composition according to the present invention, the synthetic aluminum silicate preferably has a specific surface area of 400 m2/g or more.
  • A wire coating material according to the present invention contains the vinyl chloride resin composition according to the present invention.
    • Advantages
  • The present invention can provide a vinyl chloride resin composition having a high electrical resistance. Use of the vinyl chloride resin composition can provide a wire coating material having excellent electrical insulating properties.
    • Best Modes for Carrying Out the Invention
  • A vinyl chloride resin composition according to the present invention will be described in detail below.
  • A vinyl chloride resin used in the present invention can be prepared by any method, including bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Examples of the vinyl chloride resin include polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-ethylene copolymer, a vinyl chloride-propylene copolymer, a vinyl chloride-styrene copolymer, a vinyl chloride-isobutylene copolymer, a vinyl chloride-vinylidene chloride copolymer, a vinyl chloride-styrene-maleic anhydride terpolymer, a vinyl chloride-styrene-acrylonitrile copolymer, a vinyl chloride-butadiene copolymer, a vinyl chloride-isoprene copolymer, a vinyl chloride-chlorinated propylene copolymer, a vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, a vinyl chloride-maleate copolymer, a vinyl chloride-methacrylate copolymer, a vinyl chloride-acrylonitrile copolymer, vinyl chloride-vinyl ether copolymers, and blends thereof, as well as blends, block copolymers, and graft copolymers with chlorine-free synthetic resins, such as an acrylonitrile-styrene copolymer, an acrylonitrile-butadiene-styrene copolymer, an ethylenevinyl acetate copolymer, an ethylene-ethyl (meth)acrylate copolymer, and a polyester.
  • Among these vinyl chloride resins, a vinyl chloride homopolymer, (polyvinyl chloride), is particularly preferred. Use of polyvinyl chloride can provide a material having flexibility, high flame resistance, and excellent processibility.
  • A synthetic aluminum silicate having an apparent specific gravity of 7 ml/g or more used in the present invention may be any synthetic aluminum silicate having the specified apparent specific gravity and may be a commercial product, such as Kyoward 700 (manufactured by Kyowa Chemical Industry Co., Ltd.). Use of synthetic aluminum silicate having an apparent specific gravity of 7 ml/g or more can significantly improve the electrical resistance of the resin composition. Preferably, the synthetic aluminum silicate has an apparent specific gravity in the range of 8 to 10 ml/g. Preferably, the synthetic aluminum silicate has a specific surface area of 400 m2/g or more. It is assumed that such synthetic aluminum silicate can efficiently trap impurities that reduce the electrical resistance in the resin. More preferably, the synthetic aluminum silicate has a specific surface area in the range of 500 to 800 m2/g.
  • The content of synthetic aluminum silicate in the resin composition according to the present invention ranges from 0.1 to 3 parts by weight, preferably 0.2 to 1 part by weight, per 100 parts by weight of a vinyl chloride resin. At a content of synthetic aluminum silicate below 0.1 parts by weight, the electrical resistance is not sufficiently improved. On the other hand, at a content of synthetic aluminum silicate above 3 parts by weight, the electrical resistance is not significantly improved, and the color of the resin composition deteriorates.
  • A vinyl chloride resin composition according to the present invention may contain a plasticizer, a metal salt compound, such as a barium-zinc stabilizer, a calcium-zinc stabilizer, a tin stabilizer, or a lead stabilizer, a hydrotalcite compound, a β-diketone compound, perchlorate, an organic phosphite compound, a phenol or sulfur antioxidant, an epoxy compound, a polyol compound, a hindered amine compound, an ultraviolet absorber, a filler, and a stabilization aid, which are commonly used in vinyl chloride resin compositions.
  • The plasticizer may be a plasticizer commonly used for vinyl chloride resin and includes phthalate plasticizers, such as dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, dilauryl phthalate, ditridecyl phthalate, dioctadecyl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate; adipate plasticizers, such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, and di(butyl diglycol) adipate; phosphate plasticizers, such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri(isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri(butoxyethyl) phosphate, octyldiphenyl phosphate, phenol resorcinol polyphosphate, and phenol bisphenol A polyphosphate; polyester plasticizers composed of a polyhydric alcohol, a dibasic acid, and, if necessary, a monohydric alcohol and/or a monocarboxylic acid as a stopper, the polyhydric alcohol being ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propylene glycol, 1,5-hexanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, or dipentaerythritol, the dibasic acid being oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, or terephthalic acid; epoxidized vegetable oils such as epoxidized soybean oil and epoxidized castor oil; tetrahydrophthalic acid plasticizers; azelaic acid plasticizers; sebacic acid plasticizers; stearic acid plasticizers; citric acid plasticizers; trimellitic acid plasticizers; pyromellitic acid plasticizers; and biphenylene polycarboxylic acid plasticizers.
  • The amount of the plasticizer generally ranges from 30 to 100 parts by weight, preferably 40 to 80 parts by weight, more preferably 45 to 70 parts by weight, per 100 parts by weight of a vinyl chloride resin. Less than 30 parts by weight of the plasticizer may have insufficient plasticizing effect. On the other hand, more than 100 parts by weight of the plasticizer may result in insufficient strength of the resulting vinyl chloride resin composition, and therefore the vinyl chloride resin composition may become unusable for practical applications.
  • Examples of the metal salt compound include organic carboxylates, such as stearates, laurates, oleates, maleate, and benzoates, phosphates, such as stearyl phosphate, distearyl phosphate, phenyl phosphate, and diphenyl phosphate, and basic salts, carbonates, and sulfates thereof, and basic salts, metal oxides, and metal hydroxides thereof. These compounds may be used alone or as a mixture thereof, or occasionally a complex thereof.
  • The hydrotalcite compound is preferably a double salt compound composed of magnesium and/or zinc and aluminum having the following general formula (I). Water of crystallization of the hydrotalcite compound may be removed.

            Mgx1Znx2Al2·(OH)2(x1+x2)+4·(CO3)1-y1/2·mH2O     (I)

    (wherein x1, x2, and y1 satisfy the following formula: 0 ≤ x ⁢ 2 / x ⁢ 1 ≤ 10 , 2 ≤ x ⁢ 1 + x ⁢ 2 < 20 , and 0 ≤ y ⁢ 1 ≤ 2 ,
    Figure imgb0001
    and m denotes zero or an integer.)
  • The hydrotalcite compound may be a natural or synthetic compound. The synthetic compound may be prepared by a known synthesis method described in Japanese Examined Patent Application Publications No. 46-2280 , 50-30039 , 51-29129 , 3-36839 , as well as Japanese Unexamined Patent Application Publications No. 61-174270 , 2001-164042 , 2002-53722 and the like. In the present invention, the hydrotalcite compound may have any crystal structure and any crystal particle size. Residual heavy metals, such as iron, in the raw materials of the hydrotalcite compound are preferably minimized at practical refining costs.
  • The hydrotalcite compound may be coated with a higher fatty acid, such as stearic acid, a higher fatty acid metal salt, such as an alkali metal oleate, an organic sulfonate metal salt, such as an alkali metal salt of dodecylbenzenesulfonic acid, a higher fatty acid amide, a higher fatty acid ester, or wax.
  • Examples of the β-diketone compound include acetylacetone, triacetylmethane, 2,4,6-heptatrione, butanoylacetylmethane, lauroylacetylmethane, palmitoylacetylmethane, stearoylacetylmethane, phenylacetylacetylmethane, dicyclohexylcarbonylmethane, benzoylformylmethane, benzoylacetylmethane, dibenzoylmethane, octylbenzoylmethane, bis(4-octylbenzoyl)methane, benzoyldiacetylmethane, 4-methoxybenzoylbenzoylmethane, bis(4-carboxymethylbenzoyl)methane, 2-carboxymethylbenzoylacetyloctylmethane, dehydroacetic acid, cyclohexane-1,3-dione, 3,6-dimethyl-2,4-dioxycyclohexane-1-carboxylic acid methyl ester, 2-acetylcyclohexanone, dimedone, and 2-benzoylcyclohexane. Metal salts of these β-diketone compounds may also be used. Examples of metals for use in β-diketone metal salts include alkali metals, such as lithium, sodium, and potassium; alkaline earth metals, such as magnesium, calcium, strontium, and barium; and zinc, aluminum, tin, and alkyltin.
  • Examples of perchlorate include sodium perchlorate, potassium perchlorate, barium perchlorate, ammonium perchlorate, and hydrotalcite treated with perchloric acid.
  • Examples of the organic phosphite compound include triphenyl phosphite, tris(2,4-ditert-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, tris(mono- and di-nonylphenyl) phosphite, diphenyl acid phosphite, 2,2'-methylenebis(4,6-ditert-butylphenyl)2-ethylhexyl phosphite, diphenyldecyl phosphite, phenyldiisodecyl phosphite, tributyl phosphite, tris(2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis(neopentyl glycol)·1,4-cyclohexanedimethyl diphosphite, bis(2,4-ditert-butylphenyl)pentaerythritol diphosphite, bis(2,6-ditert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, tetra(C12 to C15 mixed alkyl)-4,4'-isopropylidenediphenyl diphosphite, tetratridecyl·4,4'-butylidene bis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)·1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane·triphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 2-butyl-2-ethyl-1,3-propanediol·2,4,6-tri-tertbutylphenol-monophosphite.
  • Examples of the phenol antioxidant include 2,6-ditert-butyl-4-methylphenol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl(3,5-ditert-butyl-4-hydroxyphenyl) propionate, distearyl(3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene bis[(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2-methyl-4,6-bis(octylthiomethyl)phenol, 2-(3,5-ditert-butyl-4-hydroxyphenyl)amino-4,6-bis(octylthio)-s-triazine, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid]glycol ester, 4,4'-butylidene bis(5-tert-butyl-4-hydroxy-2-methylphenyl), 2,2'-ethylidene bis(4,6-ditert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl] terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris(3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(3,5-ditert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)propionyloxyethyl] isocyanurate, tetrakis[3-(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxymethyl]methane, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, 2-tert-amyl-4-methyl-6-[1-(2-acryloyloxy-3-tert-amyl-5-methylphenyl) ethyl]phenol, 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, and triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].
  • Examples of the sulfur antioxidant include dialkyl thiodipropionate, such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and myristylstearyl thiodipropionate, and β-alkyl mercaptopropionates of polyols, such as pentaerythritol tetra(3-dodecyl mercaptopropionate).
  • Examples of the epoxy compound include epoxidized animal and vegetable oils, such as epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, and epoxidized safflower oil, epoxidized methyl stearate, epoxidized butyl stearate, epoxidized 2-ethylhexyl stearate, epoxidized stearyl stearate, epoxidized polybutadiene, tris(epoxypropyl) isocyanurate, epoxidized tall oil fatty acid esters, epoxidized linseed oil fatty acid esters, bisphenol A diglycidyl ether, vinylcyclohexene diepoxide, dicyclohexene diepoxide, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate.
  • Examples of the polyol compound include trimethylolpropane, ditrimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, and polypentaerythritol, partial esters of these polyol compounds and fatty acids, such as stearic acid, bis(dipentaerythritol) adipate, tris(2-hydroxyethyl) isocyanurate, and saccharides, such as sorbitol and mannitol.
  • Examples of the hindered amine compound include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/diethyl succinate polycondensates, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/dibromoethane polycondensates, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-morpholino-s-triazine polycondensates, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-tert-octylamino-s-triazine polycondensates, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazine-6-yl]-1,5,8,12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine-6-ylamino]undecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazine-6-ylamino]undecane, and 3,9-bis[1,1-dimethyl-2-[tris(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)butylcarbonyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.
  • Examples of the ultraviolet absorber include benzotriazoles, such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-ditert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole, and 2,2'-methylenebis(4-tert-octyl-6-benzotriazolyl)phenol; 2-hydroxybenzophenones, such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); benzoates, such as phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, and hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; substituted oxanilides, such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; cyanoacrylates, such as ethyl-α-cyano-β,β-diphenyl acrylate and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl) acrylate; and triaryltriazines, such as 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-ditert-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-ditert-butylphenyl)-s-triazine, and 2-(2-hydroxy-4-(2-ethylhexanoyloxy) ethoxyphenyl)-4,6-diphenyl-s-triazine.
  • Examples of the filler include calcium carbonate (heavy, light, and precipitated), gypsum, titanium oxide, barium sulfate, alumina, hydrocalumite, sodium silicate, magnesium silicate, aluminum silicate, calcium silicate, zeolite, silica stone, diatomaceous earth, activated clay, talc, mica, clay, colcothar, rock wool, graphite, and carbon black. In particular, calcium carbonate is preferred because of its insignificant adverse effect on the weatherability of a vinyl chloride resin.
  • Examples of the stabilization aid include diphenylthiourea, anilinodithiotriazine, melamine, benzoic acid, cinnamic acid, p-tert-butylbenzoic acid, anhydrous silicic acid, silicate, and zeolite.
  • If necessary, a resin composition according to the present invention may contain additive agents commonly used for vinyl chloride resin, for example, a cross-linker, an antistatic agent, an anti-fogging agent, an anti-plate-out agent, a surface-treating agent, a lubricant, a flame retardant, a fluorescent agent, a fungicide, a bactericide, a foaming agent, a metal deactivator, a mold-release agent, a pigment, a processing aid, an antioxidant, and a light stabilizer.
  • A resin composition according to the present invention can be used independently of the method for processing a vinyl chloride resin and can be preferably used, for example, in roll processing, extrusion, casting, and pressure forming.
  • In particular, a vinyl chloride resin composition according to the present invention can be preferably used as a wire coating material and exhibit excellent electrical insulating properties.
    • EXAMPLES
  • The present invention will be further described in the following examples. However, the present invention is not limited to these examples.
    • <Examples 1 and 2 and Comparative Examples 1 and 2>
  • A compound shown in Table 1 was kneaded with a rolling mill at 160°C and 30 rpm for 5 minutes and was pressed at 190°C for 5 minutes to form a sheet having a thickness of 1 mm. A test specimen was prepared from the sheet and was subjected to a volume resistivity test (VR) [Ωcm] in accordance with JIS K 6723.
  • Table 2 shows the results. [Table 1]
    Compound Parts by weight
    Vinyl chloride resin 100
    Diisononyl phthalate 50
    Heavy calcium carbonate 20
    Hydrotalcite 3.5
    Zinc stearate 0.7
    Dibenzoylmethane 0.1
    Tetrakis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane 0.1
    Sorbitol 0.05
    Inorganic additive agent shown in Table 2 See Table 2
    Figure imgb0002
  • The results of Example 1 and Comparative Example 1 in Table 1 clearly show that synthetic aluminum silicate having an apparent specific gravity of 7 ml/g or more significantly improves the volume resistivity, as compared with synthetic aluminum silicate having a small apparent specific gravity. The results of Example 2 and Comparative Example 2 show that this tendency is enhanced with an increase in the content of synthetic aluminum silicate. Thus, it is clear that synthetic aluminum silicate having an apparent specific gravity of 7 ml/g or more is an excellent electrical resistance improver for vinyl chloride resin.

Claims (3)

  1. A vinyl chloride resin composition comprising 0.1 to 3 parts by weight of synthetic aluminum silicate per 100 parts by weight of a vinyl chloride resin, the synthetic aluminum silicate having an apparent specific gravity of 7 ml/g or more.
  2. The vinyl chloride resin composition according to Claim 1, wherein the synthetic aluminum silicate has a specific surface area of 400 m2/g or more.
  3. A wire coating material comprising the vinyl chloride resin composition according to Claim 1 or 2.
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